This review discusses the limitations and development of organic–inorganic polymer electrolyte membranes in the field of advanced fuel cell technology. The key achievements and challenges of hybrid membranes are extensively discussed, including the limitations of fluorinated and sulfonated membranes in terms of the durability of the energy system. The state‐of‐the‐art of advanced proton exchange membranes is high‐acidic intercalation for proton transfer through hydrogen bonding in metal–organic ligand polymer membranes. Metal–organic ligand polymer membranes are desirable for their unique feasibility of proton transfer through hydrogen bond in anhydrous environments. Organic acid moiety ligands functionalized with a metal or metal oxide have received significant attention because of their high proton conductivity and the stability of membranes. Metal–organic polymer membranes promise high proton conductivity owing to intramolecular proton transfer. Organic ligand polymers comprise mainly heterocyclic compounds, which provide spatial arrangements of acid moieties and periodic pattern morphologies due to hydrogen bonding. Metal oxide–organic ligand membranes are highly suitable for high temperature applications in terms of chemical stability. Methods of synthesis and the characteristics of metal–organic ligand polymer systems are described in this review. It is of interest to note that proton exchange membranes (PEM) could attain single active redox molecules through hydrogen bonding.